Tion of styrol and its homologues



sept. 4, 1928.

L OSTROMISLENSKY IPoxnnuzruzlsm sTYRoL AND I'rs HoloLoGUEs AND PnocsssFon THE SHnOH BWLL @Twan/tofu IwAN OSTROMISLENSKY Patented Sept. 4,1928.

UNITED STATES PATENT OFFICE.

IWAN OSTROMISLENSKY, OF NEW YORK, N, Y., ASSIGNOR TO THE NAUGATUCK CHEM-ICAL COMPANY, 0F NAUGATUCK, CONNECTICUT, A CORPORATION OF CONNECTICUT.

POLYMERIZED STYROL AND ITS HOMOLOGUES AND PROCESS FOR THE POLYMERIZA-TION OF STYROL AND ITS HOMOLOGUES.

Original application led July 12, 1924, Serial No. 725,658. Divided andthis application led January 30,

This invention relates to polymerized styrol and its homologues and toprocesses for the polymerization of styrol and its homologues.

This application .is a division of my copending application Serial No.725,658, filed July 12, 1924.

The object of the invention is to provide products having a considerablerange ot characteristics, and particularly products which are hereincalledpolymerized ArCH CHZ, where Ar is aryl, and more specificallykpolymerized styrol. These products resemble Celluloid and bakelite butditi'er from these products in that the polymers are free from theformer of high combustibility. Furthermore the polymers are moretransparent than celluloid and bakelite and when freshly made have atransparency about equal to that of ordinary glass. The polymers ofArCHzCH2 can be molded in their final form, an advantage which neitherCelluloid nor bakelite possess, since they require a chemical reactionat the time of molding in the case of bakelite or in the subsequentevaporation of a solvent in the case of Celluloid. Another object of theinvention is to provide simple and inexpensive processes for thepolymerization of such materials. f'

This application is a continuation in part of application Serial No.648, 803, tiled June 30, 1923, and describes among others products whichmay result from the process described in copending applications SerialNos. 711,584, and. 711,585, both tiled May 7, 1924.

The application Serial No. 648,803, tiled J une 30, 1923, describes thepolymerization of crude styrol, depolymerizing the solid product thusobtained, removing impurities, and rcpolymerizing the purified styrolrecovered therefrom. This application also includes depolymerizing Wastemeta styrol for purposes oi' utilizing the styrol therein. Theapplication Serial No. 711,584 is a continuation in part of Serial No.648,803 and is concerned with the polymerization of an impure styrol toa brittle product, depolymerizing the brittle product, and separatingthe majority of non-styrol hydrocarbons, and repolymcrizing the styrolportion to a tough transparent product. Application Serial No. 5,893.

Serial No. 711,585 describes a method for obtaining a tough, transparentpolymerized styrol from a styrol solution or mixture Which contains atleast 40% of unpolymerized styrol by polymerizing at 135-200 C. withaccess of air.

The invention accordingly comprises polymerized ArCHzCI-I2 Where Ar isaryl, and includes polymerized styrol which I prefer to designate hereinas beta meta ArCHzCH2 and beta meta styrol respectively. The term metaas herein employed in the expression alpha meta styrol and the like doesnot designate the position of a group but refers rather to thepolymerized form of styrol etc. The group ot' substances characterizedas alpha meta ArCHrCH2 and alpha meta styrol form the subject matter ofcopending application Serial No. 725,658, filed July 12, 1924. Theproperties which distinguish these substances will be described indetail later in the specification. The invention also includes processesfor the polymerization of beta meta ArCHzCH2 and beta meta styrol andits homologues.

Beta nieta styrol may be formed from styrol of approximately 92% purityand the homologues of beta meta styrol may be formed from ArCI'LCH,Where Ar is aryl.

`By exposing styrol in a suitable quantity to the action of heat for asuieient length of time beta nieta styrol is formed. Thev temperatureand time required to produce beta meta styrol is in general in excess ofthat required to produce the alpha modification. As stated in mycopending application Serial No. 725,658, filed July 12, 1924, theproduction of alpha meta styrol, in so far as time and temperature areconcerned. follows a fairly definite curve, which may be approximatelyexpressed by plotting the time versus temperature values 2() hrs-1400.18 hrs.YH 1550` 16 his-165", l0 hrszHlT-O. 5 hrs.Arm 175^ Thispolymerization curve is designated by the curve vl on the aeoinpanyinfl' drawing. which forms part ol' tbe present specification.Times and tiniperar tures lying well within the area bounded by thiscurve and the axisl result in the forniation of tht` alpha modifieation.Time` and temperature`l lyingi nell beyond the enrve expressed by theabove equation result in the formation of the beta modification aean airbath heated to 140 -at the end of which time cordin to the conditions inthe following examp es. The amount of beta meta styrol produced upon aslight excess of time or temperature will be relatively small fordifferent points along the above curve, but will increase as the timeand temperature for any given point along the curve are increased.

Example 1.-A specific example of the production of beta meta styrol isas follows: Styrol of upwards of 92% purity is heated in a sealed glasstube half filled with the material and placed in a horizontal position,the heating being continued for 40 hours in C. approximately,

olymerization is substantially complete Wit the product-ion of beta metastyrol. The tube may be 0.7 by 26 cm., having a volume of approximately10.0 cc. in which case the amount of st rol which may be satisfactorilyemploye about 5.0 cc.

Emample 2.-A sealed glass tube half filled with styrol of upward of 92%purity is heated for 18 hours in an air bath heated to 170 C. in ahorizontal position at the end of which time polymerization issubstantially complete with the production of beta meta styrol.

Eample 3.-Under similar conditions styrol is heated for 12 hours in abath heated to 180 C. at the end of which time polymerization issubstantially complete With the roduction of beta meta styrol.

@ample 4.-Under similar conditions styrol is heated for 22 hours in anair bath heated to 140 C. at the end of which time polymerization issubstantially complete with the production of beta meta styrol.

Example 5.-Under similar conditions styrol is heated for 2% hours inpanair bath heated to 185 C. at the end of which time polymerization issubstantially complete with the production of beta meta styrol.

If the styrol is heated for a shorter time than given in the examplesabove, it is apt to become a mixture of the alpha and beta modificationsin which case the vitreous product shows in some places a lustrous andin others a mat or dull fracture.

As in the case of the alpha modification the speed at which the betamodification is formed depends not only on the temperature but on theamount of styrol as Well as on the shape of the vessel in which thepolymerization is carried out. I have often observed that when thesealed glass tube is placed in a horizontal position the polymerizationof styrol to beta meta styrol takes place much faster than when the tubestands upright. For instance When the polymerization is conducted in asealed glass tube placed in a vertical position at 180 C. beta metastyrol is formed in hours while when under similar conditions the sametube ing, at first in spots and finally the mass becomes dull andslightly translucent. The

fracture of beta'meta styrol is shiny and lustrous. It is not suscetible to cutting, sawing, planing, and phshing operations, crackingbadly when subjected to these operations. When cut with a knife it sphtsinto small grains', the surface of the cut being shiny and pitted. Whenhit With a hammer a relatively weak blow, or when dropped from arelatively inconsiderableheight it cracks. It can be readily ground to apowder in a porcelain mortar. On cooling after complete polymerizationit detaches itself from the sides of the glass vessel in which it waspolymerized Without breaking it. Heated to 100 C. it becomes appreciablymore plastic and gradually loses its shape. The transverse tensilestrength is 1000 lbs. per square inch. Upon dry distillation it producesapproximately the same results as alpha meta styrol that isA it producesas high as 70 of its Weight in styrol when heated at 375 475 C. Whentreated with bromine in the manner indicated for alpha meta styrolpractically the same result is effected as With the alpha modificationin that when in solution it does not decolorize a 3% solution of bromineat 0 C. Its reaction with prolonged treatment of hydrofluoric acid 1sthe same as for alpha modification both materials being substantiallyunchanged. The beta modification of meta styrol as prepared in the abovemanner is substantially free from unpolymerized styrol.

It should be noted that alpha meta styrol may be transformed to the betameta styrol by heating the alpha in an open vessel at normal pressure.The length of the process depends upon the quantity and shape of thepieces of the original alpha meta styrol. In vacuo the transformationproceeds faster than it does under normal pressure.

As many apparently Widely different embodiments of this invention may bemade without departing from the spirit thereof, it is to be understoodthat I do not intend to limit myself to the specific form of theinvention as set forth except as indicated in the appended claims.

Having thus described my invention, what l claim and desire to protectby Letters Patent is:

1. A process for forming beta meta styro'l llo which comprises heatingthe styrol of approximity 92% or greater purity in a substantiallyhorizontal tube for approximately 40 hrs. in an air bath heated toapproximatel 140 C.

2. s new com ounds, the beta meta styrols, substantie` ly colorlesstransparent substances having ashiny, lustrous fracture, splitting into.grains when cut, detachable from the sides of a glass polymerizingvessel without breaking the vessel, and easily reducible to a powder byinding, said compounds being substantial y free of unpoymerized styrols.

igned at Cromwell, county of Middlesex, und State of Connecticut this26th day of January, 1925.

IWAN OSTROMISLENSKY.

